Approximate Rate Constants Research Articles

Study of the Mechanism of 7‐exo‐trig Cyclizations of Aryl, Vinyl, and Alkyl Radicals on Oxime Ethers

AbstractIn this work, we conducted a study of 7‐exo‐trig cyclizations mechanism involving aryl, vinyl, and alkyl radicals on oxime ethers. Initially, the reaction of brominated oxime ether 9 a with (TMS)3SiH and AIBN gave rise to aryl radicals that underwent a 7‐exo‐trig cyclization on the oxime ether, yielding dibenzoxepine 10 a, and the ipso reaction and reduction products were obtained as well. Approximate rate constants at 80 °C for the 7‐exo‐trig (1.0×108 s−1) and the ipso cyclization (4.3×107 s−1) were determined by competition experiments. DFT calculations showed good agreement with the experimental results. The reduction rate constant of the N‐alkoxyaminyl radical with (TMS)3SiH was calculated to be 4.1×10−1 M−1 s−1; while the rate constants for the 7‐exo‐trig cyclizations of vinyl and alkyl radicals on the oxime ether were estimated in the ranges of 106 s−1–108 s−1 and 103 s−1–108 s−1, respectively. The 7‐exo‐trig cyclization reactions involving aryl, vinyl, and alkyl radicals with oxime ethers were found to be an exothermic and irreversible process, with the oximic carbon showing a preference for nucleophilic alkyl radicals. This kinetic study contributes to the deeper understanding of radical‐mediated cyclizations, enabling the efficient design of complex synthetic routes.

Facile preparation of bi-functional iron doped mesoporous materials and their application in the cycloaddition of CO2

Abstract Two kinds of bi-functional transition metal doped mesoporous materials (Fe-HMS and Fe-MCM-41) are prepared using one-step hydrothermal method and then treated with hydrochloric acid ethanol solution. The N2 adsorption and HRTEM results show that both of Fe-HMS and Fe-MCM-41 possess mesoporous structure. The UV–vis results suggest that the Fe species are mainly located within the framework. The basicity of as-prepared samples was studied by temperature programmed desorption using CO2 as probe molecule (CO2-TPD). The catalytic performance of Fe-HMS and Fe-MCM-41 in CO2 cycloaddition largely depends on the amount of the accessible basic sites. The acid–base active sites, framework Fe and PDDA species cooperatively catalyze the CO2 cycloaddition for the production of cyclic carbonates under the condition without any co-catalyst. The conversion of epichlorohydrin (ECH) is 97.4% and the selectivity of chloropropene carbonate is 92.9% under optimal conditions. The approximate rate constant of cycloaddition reaction of CO2 with ECH under optimum reaction temperature is calculated. It is worth noting that the Fe-HMS material shows superior reusability than Fe-MCM-41. In addition, this work provides a facile way on the synthesis of bi-functional acid–base heterogeneous catalyst with outstanding catalytic performance for the fixation of CO2.

Polymer-Supported Zn-Containing Imidazolium Salt Ionic Liquids as Sustainable Catalysts for the Cycloaddition of CO2: A Kinetic Study and Response Surface Methodology

Metal-containing ionic liquids (MIL) are highly active homogeneous catalysts for the chemical fixation of CO2 into epoxides yielding five-membered cyclic carbonates. To obtain sustainability, polymer-supported MIL catalysts were designed to overcome their previously reported inherent poor recoverability. Polymer-supported Zn-containing imidazolium salts, PS-(Im)2ZnX2, possessing bifunctional properties were identified as sustainable catalysts for the activation of CO2 under solvent-free conditions. PS-(Im)2ZnX2 showed good catalytic performance and was readily recoverable and reusable in the subsequent reaction cycles for the cycloaddition of CO2 to propylene oxide. Kinetic studies for the cycloaddition of CO2 to propylene carbonate using batch or semibatch systems were performed to calculate the approximate rate constants, which provide an explanation for the different reaction systems. In addition, process optimization using the response surface methodology was performed, and the interactions between th...

금속 함유 이온성 액체 촉매상에서의 프로필렌 카보네이트의 합성

본 연구에서는 세 가지 형태의 금속을 함유한 이온성 액체 촉매를 제조하고, 다양한 물리화학적 분석법으로 제조된 촉매의 특성분석을 실시하였다. 프로필렌 옥사이드(PO)와 이산화탄소의 부가반응을 통한 프로필렌 카보네이트(PC)의 합성반응에서 세 가지 촉매의 반응활성을 확인하였고 속도론적 연구를 통해 촉매들의 반응성 차이를 비교하였다. 세가지 금속이 다른 촉매에 대한 유사 반응속도 상수(<TEX>$K_{app}$</TEX>)는 <TEX>$(MeIm)_2ZnCl_2$</TEX>, > <TEX>$(MeIm)_2FeCl_2$</TEX> > <TEX>$(MeIm)_2CuCl_2$</TEX>의 순서이며, 이 것은 세 가지 촉매의 반응성이 <TEX>$(MeIm)_2ZnCl_2$</TEX> > <TEX>$(MeIm)_2FeCl_2$</TEX> > <TEX>$(MeIm)_2CuCl_2$</TEX>의 순서로 실험결과와 잘 일치하였다. In this study, three different metal-containing ionic liquid catalysts were prepared by metal insertion and characterized by various physicochemical analytic methods. The catalytic performance of the metal containing ionic liquids in the cycloaddition of <TEX>$CO_2$</TEX> with propylene oxide (PO) to produce propylene carbonate (PC) was investigated under the solvent free condition. The order of approximate rate constants (<TEX>$K_{app}$</TEX>) for the metal containing ionic liquid catalysts was <TEX>$(MeIm)_2ZnCl_2$</TEX>, > <TEX>$(MeIm)_2FeCl_2$</TEX> > <TEX>$(MeIm)_2CuCl_2$</TEX>. These results are in accord with the experimentally obtained activity order of the different metal containing ionic liquid catalysts.

Kinetic Model of Mg2+ Induced RNA Tertiary Folding from Stopped Flow Fluorescence Data

Many of the biological processes that involve RNA rely on its ability to form complex tertiary structures. The process of how these molecules fold into these tertiary structures is not well understood, in part due to the unpredictability and complexity of the interactions among nucleotides that define the tertiary structures. To better understand RNA folding we are investigating the prokaryotic rRNA GTPase center, a 60 nucleotide RNA which folds in to a complex tertiary structure in the presence of Mg2+ ions. Its tertiary interactions include formation of base triples, a triloop, as well as long-range nucleobase stacking interactions. To monitor its folding process we have replaced key adenine residues with the fluorescent base analog 2-aminopurine in different positions of this RNA to probe distinct local environments. Stopped flow kinetics techniques were used to examine the coordination of these different elements in the context of global folding. Data from the stopped flow experiments were used to refine a theoretical model of the folding pathway of this RNA. Our model consists of four temporally resolved kinetic steps with approximate rate constants. This work was funded by the NIH R01-GM098102 to KBH. Labeled RNA molecules were contributed by Agilent.

Competitive kinetics as a tool to determine rate constants for reduction of ferrylmyoglobin by food components

Competitive kinetics were applied as a tool to determine apparent rate constants for the reduction of hypervalent haem pigment ferrylmyoglobin (MbFe(IV)O) by proteins and phenols in aqueous solution of pH 7.4 and I=1.0 at 25°C. Reduction of MbFe(IV)O by a myofibrillar protein isolate (MPI) from pork resulted in kMPI=2.2±0.1×104M−1s−1. Blocking of the protein thiol groups on the MPI by N-ethylmaleimide (NEM) markedly reduced this rate constant to kMPI-NEM=1.3±0.4×103M−1s−1 consistent with a key role for the Cys residues on MPI as targets for haem protein-mediated oxidation. This approach allows determination of apparent rate constants for the oxidation of proteins by haem proteins of relevance to food oxidation and should be applicable to other systems. A similar approach has provided approximate apparent rate constants for the reduction of MbFe(IV)O by catechin and green tea extracts, though possible confounding reactions need to be considered. These kinetic data suggest that small molar excesses of some plant extracts relative to the MPI thiol concentration should afford significant protection against MbFe(IV)O-mediated oxidation.

Stable Isotope Labeling of Phosphoproteins for Large-scale Phosphorylation Rate Determination

Signals that control responses to stimuli and cellular function are transmitted through the dynamic phosphorylation of thousands of proteins by protein kinases. Many techniques have been developed to study phosphorylation dynamics, including several mass spectrometry (MS)-based methods. Over the past few decades, substantial developments have been made in MS techniques for the large-scale identification of proteins and their post-translational modifications. Nevertheless, all of the current MS-based techniques for quantifying protein phosphorylation dynamics rely on the measurement of changes in peptide abundance levels, and many methods suffer from low confidence in phosphopeptide identification due to poor fragmentation. Here we have optimized an approach for the stable isotope labeling of amino acids by phosphate using [γ-¹⁸O₄]ATP in nucleo to determine global site-specific phosphorylation rates. The advantages of this metabolic labeling technique are increased confidence in phosphorylated peptide identification, direct labeling of phosphorylation sites, measurement phosphorylation rates, and the identification of actively phosphorylated sites in a cell-like environment. In this study we calculated approximate rate constants for over 1,000 phosphorylation sites based on labeling progress curves. We measured a wide range of phosphorylation rate constants from 0.34 min⁻¹ to 0.001 min⁻¹. Finally, we applied stable isotope labeling of amino acids by phosphate to identify sites that have different phosphorylation kinetics during G1/S and M phase. We found that most sites had very similar phosphorylation rates under both conditions; however, a small subset of sites on proteins involved in the mitotic spindle were more actively phosphorylated during M phase, whereas proteins involved in DNA replication and transcription were more actively phosphorylated during G1/S phase. The data have been deposited to the ProteomeXchange with the identifier PXD000680.

Trialkyl Phosphites and Diaryliodonium Salts as Co-initiators in a System for Radical-Promoted Visible-Light-Induced Cationic Polymerization

Trialkyl phosphites ((RO)3P) can act as co-initiators for the diaryliodonium-induced cationic polymerization of cyclohexene oxide (CHO) or THF. A radical initiation step is also required, consistent with the essential role of a radical chain reaction of the phosphite with the iodonium salt to form polymerization-starting aryltrialkoxyphosphonium salts (ArP(+)(OR)3). We used the visible photolysis of phenylazoisobutyronitrile (PAIBN) as the radical initiation step. The presence of multiple fluorine substituents on the phosphite, as in tris(2,2,2-trifluoroethyl) phosphite (TFP), allows polymerization to proceed with a minimal amount of chain transfer from nucleophilic attack by the phosphite. In a typical experiment, a CHO solution of bis(4-tert-butylphenyl)iodonium hexafluorophosphate (0.05 M), TFP (0.1 M), and PAIBN (0.02 M) was illuminated with a 65-W compact fluorescent bulb for 1 h, resulting in a 78% conversion to poly(cyclohexene oxide) with an average molecular weight (MW) of 25000. We also used competition experiments to determine approximate rate constants for reactions of phenyl radicals with CHO (k = 2 × 10(6) M(-1) s(-1)) and with TFP (k = 2 × 10(8) M(-1) s(-1)).

A New Method for Removal of Hydrogen Peroxide Interference in the Analysis of Chemical Oxygen Demand

Many advanced oxidation processes involve addition of hydrogen peroxide (H(2)O(2)) with the aim of generating hydroxyl radicals to oxidize organic contaminants in water. However, chemical oxygen demand, a common measure of gross residual organic contamination, is subject to interference from residual H(2)O(2) in the treated water. A new method, involving catalytic decomposition of H(2)O(2) with addition of heat and sodium carbonate (Na(2)CO(3)), is proposed in this work to address this problem. The method is demonstrated experimentally, and modeled kinetically. Results for 5 mM H(2)O(2) in deionized (DI) water included reduction to below the COD detection limit after 60 min heating (90(◦)C) with addition of 20 g/L Na(2)CO(3) concentrated solution, whereas 900 min were required in treated municipal wastewater. An approximate second order rate constant of 11.331 M(-1)·min(-1) at Na(2)CO(3) dosage of 20 g/L was found for the tested wastewater. However, kinetic modeling indicated a two-step reaction mechanism, with formation of peroxocarbonate (CO(4)(2-)) and ultimate decomposition to H(2)O and O(2) in pure H(2)O(2) solution. A similar mechanism is apparent in wastewater at high catalyst concentrations, whereas at low Na(2)CO(3) addition rates, the catalytic effects of other constituents appear important.

The influence of reversible trianionic pincer OCO3−μ-oxo Crivdimer formation ([Criv]2(μ-O)) and donor ligands in oxygen-atom-transfer (OAT)

The oxygen-atom-transfer (OAT) from [(t)BuOCO]Cr(V)(O)(THF) (2) (where (t)BuOCO = [2,6-C(6)H(3)(6-(t)BuC(6)H(3)O)(2)](3-), THF = tetrahydrofuran) to triphenylphosphine (PPh(3)) in THF produces [(t)BuOCO]Cr(III)(THF)(3) (1) and triphenylphosphine oxide (OPPh(3)) at a rate of 69.5(±1.9) M(-1) s(-1) (22 °C). Identical rate constants were attained when acetonitrile (MeCN) and dichloromethane/THF (CH(2)Cl(2)/THF) were used as solvents. Electron paramagnetic resonance (EPR) data shows that the six-coordinate complex, [(t)BuOCO]Cr(V)(O)(THF)(2) (2a) forms upon addition of THF to 2, suggesting 2a as the active OAT species in THF. Similarly, addition of OPPh(3) has no influence on the rate of OAT, but the addition of triphenylphosphorus ylide (CH(2)PPh(3)) to form [(t)BuOCO]Cr(V)(O)(CH(2)PPh(3)) (4) prevents OAT to PPh(3). In CH(2)Cl(2), a [Cr(IV)](2)(μ-O) intermediate forms during the OAT from 2 to PPh(3). The OAT from {[(t)BuOCO]Cr(IV)(THF)}(2)(μ-O) (3) to PPh(3) reveals a zero-order dependence in PPh(3) indicating the dimer must first dissociate prior to OAT. The decay of 3versus time does not follow first-order kinetics due to the formation of a [(t)BuOCO]Cr(III)(THF) species (5) that inhibits the dissociation of 3. The change in concentration of 3versus time during OAT was simulated to obtain approximate rate constants.

State-to-State Quantum Dynamics Calculations of the C + OH Reaction on the Second Excited Potential Energy Surface

Accurate three-dimensional quantum-mechanical scattering calculations using a time-indepedent hyperspherical method have been performed for the C((3)P) + OH(X(2)Π) → CO(a(3)Π) + H((2)S) reaction on the second excited potential energy surface of 1(4)A″ symmetry. State-to-state reaction probabilities at a total angular momentum J = 0 have been computed in a wide range of collision energies. Many pronounced resonances have been found, espcially at low energy. The product vibrational distributions are noninverted. The present results therefore suggest that the title reaction proceeds via a long-lived intermediate complex. An approximate quantum-mechanical rate constant has also been calculated, and large differences are observed with the quasi-classical trajectory prediction.

UV-induced photodegradation of oseltamivir (Tamiflu) in water

Environmental contextOseltamivir (Tamiflu) is widely used to prevent and treat influenza but conventional wastewater processes involving sedimentation and biotic oxidation do not appear to significantly remove it from sewage, leading to its discharge into the environment. A range of advanced oxidation processes (AOPs) involving photolysis of aqueous solutions of oseltamivir with UV alone, UV/H2O2 and UV/H2O2/FeII is demonstrated to lead to photodegradation of oseltamivir to products with no ecotoxicity observed. These AOPs may therefore offer potentially environmentally friendly sewage water treatment options. AbstractAqueous solutions of the antiviral drug oseltamivir phosphate (OSP, Tamiflu, (3R,4R,5S)-ethyl 4-acetamido-5-amino-3-(pentan-3-yloxy)cyclohex-1-enecarboxylate) were degraded using advanced oxidation processes (AOPs) involving photodegradation with UV alone, UV/H2O2 and UV/H2O2/FeII (photo-Fenton reaction). The photodecay of the parent OSP in all three cases followed first-order kinetics with respective rate constants of 0.21, 1.56 and 1.75 min–1 at 20°C in pH 7 phosphate-buffered Milli-Q water. The rate of UV/H2O2 photolysis in the presence of 2-methylpropan-2-ol was significantly slower with an approximate first-order rate constant of 0.13 min–1 suggesting the involvement of •OH in the degradation process. NMR spectroscopy, mass spectrometry and high-performance liquid chromatography (HPLC) with UV diode array detection were used to identify the crude photoproduct as the hydroxylated OSP derivative (3S,4R,5S)-ethyl 4-acetamido-5-amino-2-hydroxy-3-(pentan-3-yloxy)cyclohexanecarboxylate that occurs by an unknown mechanism. OSP and this crude photoproduct demonstrated no effect on the survival of Quinquelaophonte sp. over 96 h.

Calculation of reaction rate constants using approximate evolution of quantum trajectories in imaginary and real time

Reaction rate constants can be directly obtained from evolution of the flux operator eigenvectors under the Boltzmann and Hamiltonian operators. This is achieved by evolving the quantum trajectory ensemble, representing a wavefunction, in imaginary time seamlessly switching to the real-time dynamics. Quantum–mechanical effects are incorporated through the quantum potential dependent on the trajectory momenta or on the derivatives of the wavefunction amplitude. For practicality the quantum potential and wavefunction nodes are described using linear basis, which is exact for Gaussian wavefunctions. For the Eckart barrier approximate rate constants show significant improvement over the parabolic barrier rate constants.

An NMR Study of the Equilibration of d‐Glucaric Acid with Lactone Forms in Aqueous Acid Solutions

The aqueous solution equilibration of d‐glucaric acid with its lactone forms was studied by NMR with and without acid catalysis. The kinetics of the approach to equilibrium were simulated, and approximate equilibrium and rate constants were obtained.

Accurate and approximate thermal rate constants for polyatomic chemical reactions

In favourable cases it is possible to calculate thermal rate constants for polyatomic reactions to high accuracy from first principles. Here, we discuss the use of flux correlation functions combined with the multi-configurational time-dependent Hartree (MCTDH) approach to efficiently calculate cumulative reaction probabilities and thermal rate constants for polyatomic chemical reactions. Three isotopic variants of the H2 + CH3 → CH4 + H reaction are used to illustrate the theory. There is good agreement with experimental results although the experimental rates generally are larger than the calculated ones, which are believed to be at least as accurate as the experimental rates. Approximations allowing evaluation of the thermal rate constant above 400 K are treated. It is also noted that for the treated reactions, transition state theory (TST) gives accurate rate constants above 500 K. TST theory also gives accurate results for kinetic isotope effects in cases where the mass of the transfered atom is unchanged. Due to neglect of tunnelling, TST however fails below 400 K if the mass of the transferred atom changes between the isotopic reactions.

Approximate Rate Constants for Nonideal Diffusion and Their Application in a Stochastic Model

Rate constants are presented for diffusion in dilute nonideal solutions with or without the presence of a spatially varying potential field. Expressions for the rate constants have been derived by earlier workers, and essentially the same derivation is reviewed and expanded in this paper to justify the expressions used for the rate constants. The diffusion rate constants are used in a random walker model to demonstrate how solution nonidealities can be captured accurately using this approach. Examples are presented of ideal solute diffusion as well as nonideal diffusion of nonelectrolytes and simple electrolytes in water. The use of the approach to simulate advection is described, and a possible strategy for extending the approach to more concentrated solutions is briefly discussed.

Accurate quantum calculations of the reaction rates for H∕D+CH4

In previous work [T. Wu, H. J. Werner, and U. Manthe, Science 306, 2227 (2004)], accurate quantum reaction rate calculations of the rate constant for the H+CH4-->CH3+H2 reaction have been presented. Both the electronic structure calculations and the nuclear dynamics calculations are converged with respect to the basis sets employed. In this paper, the authors apply the same methodology to an isotopic variant of this reaction: D+CH4-->CH3+HD. Accurate rate constants are presented for temperatures between 250 and 400 K. For temperatures between 400 and 800 K, they use a harmonic extrapolation to obtain approximate rate constants for H/D+CH4. The calculations suggest that the experimentally reported rate constants for D+CH4 are about a factor of 10-20 too high. For H+CH4, more accurate experiments are available and agreement is much better: the difference is less than a factor of 2.6. The kinetic isotope effect for the H/D+CH4 reactions is studied and compared with experiment and transition state theory (TST) calculations. Harmonic TST was found to provide a good description of the kinetic isotope effect.

NO•Release from MbFe(II)NO and HbFe(II)NO after Oxidation by Peroxynitrite

In this work, we showed that the reaction of peroxynitrite with MbFe(II)NO, in analogy to the corresponding reaction with HbFe(II)NO (Herold, S. Inorg. Chem. 2004, 43, 3783-3785), proceeds in two steps via the formation of MbFe(III)NO, from which NO* dissociates to produce iron(III)myoglobin (Mb = myoglobin; Hb = hemoglobin). The second-order rate constants for the first steps are on the order of 10(4) and 10(3) M(-1) s(-1), for the reaction of peroxynitrite with MbFe(II)NO and HbFe(II)NO, respectively. For both proteins, we found that the values of the second-order rate constants increase with decreasing pH, an observation that suggests that HOONO is the species responsible for oxidation of the iron center. Nevertheless, it cannot be excluded that the pH-dependence arises from different conformations taken up by the proteins at different pH values. In the presence of 1.2 mM CO2, the values of the second-order rate constants are larger, on the order of 10(5) and 10(4) M(-1) s(-1), for the reaction of peroxynitrite with MbFe(II)NO and HbFe(II)NO, respectively. The pH-dependence of the values for the reaction with MbFe(II)NO suggests that ONOOCO2- or the radicals produced from its decay (CO3*-/NO2*) are responsible for the oxidation of MbFe(II)NO to MbFe(III)NO. In the presence of large amounts of nitrite (in the tens and hundreds of millimoles range), we observed a slight acceleration of the rate of oxidation of HbFe(II)NO by peroxynitrite. A catalytic rate constant of 40 +/- 2 M(-1) s(-1) was determined at pH 7.0. Preliminary studies of the reaction between nitrite and HbFe(II)NO showed that this compound also can oxidize the iron center, albeit at a significantly slower rate. At pH 7.0, we obtained an approximate second-order rate constant of 3 x 10(-3) M(-1) s(-1).

Asymmetric Radical Cyclization Reactions of Axially Chiral N‐Allyl‐o‐iodoanilides to Form Enantioenriched N‐Acyl Dihydroindoles.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Asymmetric radical cyclization reactions of axially chiral N-allyl- o-iodoanilides to form enantioenriched N-acyl dihydroindoles

Radical cyclizations of enantiomerically enriched N-allyl- o-iodoanilides provide N-acyl-3-alkyl-2,3-dihydroindoles in good yields and with good to excellent levels of chirality transfer from the N–Ar axis to the new stereocenter. In competitive cyclizations of N-acryloyl- N-allyl- o-iodoanilides, the addition of an o-methyl group reverses the regioselectivity of the radical cyclization from the acryloyl group to the allyl group. Approximate rate constants for representative radical cyclizations have been measured to provide insight into the origin of these observations.